EP2797742B1 - Retortable easy opening seals for packaging film - Google Patents
Retortable easy opening seals for packaging film Download PDFInfo
- Publication number
- EP2797742B1 EP2797742B1 EP12815966.2A EP12815966A EP2797742B1 EP 2797742 B1 EP2797742 B1 EP 2797742B1 EP 12815966 A EP12815966 A EP 12815966A EP 2797742 B1 EP2797742 B1 EP 2797742B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- film
- outer layer
- ethylene
- inner portion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920006280 packaging film Polymers 0.000 title 1
- 239000012785 packaging film Substances 0.000 title 1
- 239000010410 layer Substances 0.000 claims description 86
- 229920000642 polymer Polymers 0.000 claims description 66
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 36
- 239000005977 Ethylene Substances 0.000 claims description 32
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- -1 polypropylene Polymers 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 19
- 239000004743 Polypropylene Substances 0.000 claims description 16
- 229920001155 polypropylene Polymers 0.000 claims description 16
- 229920001519 homopolymer Polymers 0.000 claims description 11
- 229920001684 low density polyethylene Polymers 0.000 claims description 11
- 239000004702 low-density polyethylene Substances 0.000 claims description 11
- 229920005604 random copolymer Polymers 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- IKZZIQXKLWDPCD-UHFFFAOYSA-N but-1-en-2-ol Chemical compound CCC(O)=C IKZZIQXKLWDPCD-UHFFFAOYSA-N 0.000 claims 1
- 229920005629 polypropylene homopolymer Polymers 0.000 claims 1
- 239000002344 surface layer Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 17
- PNAAEIYEUKNTMO-UHFFFAOYSA-N S-Seven Chemical compound C=1C=CC=CC=1P(=S)(OCC)OC1=CC=C(Cl)C=C1Cl PNAAEIYEUKNTMO-UHFFFAOYSA-N 0.000 description 16
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000000565 sealant Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000178 monomer Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 229920000034 Plastomer Polymers 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000011179 visual inspection Methods 0.000 description 4
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000004148 curcumin Substances 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000007765 extrusion coating Methods 0.000 description 2
- 238000009459 flexible packaging Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000011888 snacks Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2274/00—Thermoplastic elastomer material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/552—Fatigue strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/10—Polypropylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/16—EPDM, i.e. ethylene propylene diene monomer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2333/00—Polymers of unsaturated acids or derivatives thereof
- B32B2333/04—Polymers of esters
- B32B2333/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2333/00—Polymers of unsaturated acids or derivatives thereof
- B32B2333/04—Polymers of esters
- B32B2333/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2813—Heat or solvent activated or sealable
- Y10T428/2817—Heat sealable
- Y10T428/2826—Synthetic resin or polymer
Definitions
- the invention relates to a polyolefin-based heat sealable, retortable easy opening seal.
- the invention also relates to methods of making and using the heat sealable, retortable easy opening seal.
- Heat sealable and easy-opening films are employed on a large scale for temporarily closing containers that include, for example, food products. During use, a consumer tears away the peelable film. To gain consumer acceptance, a number of characteristics associated with a heat sealable and peelable film are desired.
- Heat sealable films must be capable of being sealed upon the application of heat.
- the backing or web layer of the film comes into direct contact with a heated surface such as a sealing jaw. Heat is thus transferred through the backing layer of the film to melt and fuse the inner sealant layer to form a seal.
- the backing layer generally has a higher melting temperature than the inner sealant layer so that the backing layer of the film does not substantially melt and therefore does not stick to the heated surface.
- the seal should be capable of surviving a retort operation.
- a typical retort process subjects the sealed package to a temperature of 100°C. to 135°C. for 20 to 60 minutes or even up to 100 minutes, depending on the size of the container.
- gases are generated within the package and pressure increases greatly.
- the retort system may include an over pressure to help balance the package internal pressures, the net result will still be a pressurized package during retorting.
- the films used to seal the container must be sufficiently strong to withstand the increased internal pressure and the elevated temperatures.
- seals used in retort applications are typically difficult to open at room temperature using average manual force. It would be desirable to have a heat sealable film which could withstand the conditions of retort applications yet still be easily opened manually by a consumer.
- the force required to pull a seal apart is called “seal strength” or “heat seal strength” which can be measured in accordance with ASTM F88-94.
- the desired seal strength varies according to specific end user applications. For flexible packaging applications, such as cereal liners, snack food packages, cracker tubes and cake mix liners, the seal strength desired is generally in the range of 0.18-1.6 kilograms per centimeter.
- a seal strength in the range of 0.35-0.52 kilograms per centimeter is commonly specified, although specific targets vary according to individual manufactures requirements.
- a sealable and peelable film can also be used in rigid package applications, such as lids for convenience items (e.g., snack food such as puddings) and medical devices.
- Typical rigid packages have a seal strength of 0.18-0.9 kilograms per centimeter.
- the seal layer can be on the lid or on the container or both.
- hot tack Another desired property for the heat-sealable films is adequate "hot tack".
- the film is removed from contact with the heated surface and/or the retort process, the film is cooled to room temperature. Before the inner sealant layer is cooled to room temperature, it should be able to maintain its seal integrity.
- the ability of an adhesive or sealant layer to resist creep of the seal while it is still in a warm or molten state is generally referred to as "hot tack.” To form a good seal, the hot tack of the sealable and peelable film should be adequate.
- a broad sealing window also enables high speed packaging of heat sensitive products, as well as, provides a degree of forgiveness for changes in packaging or filling speeds.
- Additional desired characteristics for heat sealable films include a low coefficient of friction and good abuse resistance.
- a low coefficient of friction ensures that the sealant layer can be processed smoothly and efficiently on fabrication and packaging equipment and is particularly important for vertical form-fill-and-seal packaging.
- Good abuse resistance and toughness is desired, for example, in cereal box liners to withstand tears and punctures from irregularly-shaped, rigid cereals.
- Additional characteristics include taste and odor performance and barrier or transmission properties.
- the multilayer film comprises a first outer layer which is heat sealable.
- the first outer layer comprises from 95 to 100 percent (by weight of the first outer layer) of a first polymer, said first polymer being derived from propylene monomer and optionally one or more comonomers selected from the group consisting of ethylene and C 4 -C 8 alpha olefins.
- the first polymer has a melting point of at least 125°C.
- the multilayer film further comprises an inner portion adjacent to the first outer layer. The inner portion may be a single layer or may comprise several layers.
- At least one layer of the inner portion comprises an elastomeric propylene based polymer ("EPBP"). Further at least one layer of the inner portion comprises a second polymer, wherein the second polymer is selected from the group consisting of high pressure low density polyethylene, high density polyethylene, ethylene acrylic acid copolymers, ethylene (meth) acrylic acid copolymers and combinations thereof.
- the second polymer may be together with the EPBP in the same layer or may be in a separate layer. It is also contemplated that the inner portion may optionally comprise one or more additional layers, which may or may not contain EPBP or the second polymer.
- the multilayer film further comprises a second outer layer arranged so that the inner portion is encapsulated between the first outer layer and the second outer layer.
- the second outer layer comprises a third polymer, wherein said third polymer is selected from the group consisting of homopolymer polypropylene, random copolymer polypropylene and impact copolymer polypropylene and blends thereof.
- U.S. Patent Publication No. 2004/0151932 to Galloway is directed to sealant films comprising a first sealant layer which readily and easily delaminates or peels from a second adjacent film layer.
- the first sealant layer and the second adjacent layer of the sealant film comprise propylene or ethylene moieties wherein the propylene or ethylene moieties may be homopolymers or copolymers.
- the film structures can be used independently, or laminated to a second film structure wherein the second film structure may comprise a single layer or multiple layers.
- the sealant films can be heat sealed to a packaging component, such as a tray either as a single film structure or as a laminate comprising a second film structure.
- the sealant film structures may be used as retortable lidstock.
- the sealant films disclosed by Galloway do not however possess the desired retort properties.
- polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
- the generic term polymer thus embraces the term “homopolymer”, usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer” which refers to polymers prepared from two or more different monomers.
- Melt strength which is also referred to in the relevant art as “melt tension” is defined and quantified herein to mean the stress or force (as applied by a wind-up drum equipped with a strain cell) required to draw a molten extrudate at a haul-off velocity at which the melt strength plateaus prior to breakage rate above its melting point as it passes through the die of a standard plastometer such as the one described in ASTM D1238-E. Melt strength values, which are reported herein in centi-Newtons (cN), are determined using a Gottfert Rheotens at 190°C.
- the present invention relates to a multilayer film particularly well-suited for heat seals used in retort applications.
- the multilayer film comprises a first outer layer which is heat sealable.
- the first outer layer comprises from 95 to 100 percent (by weight of the first outer layer) of a first polymer, said first polymer being derived from propylene monomer and optionally one or more comonomers selected from the group consisting of ethylene and C 4 -C 8 alpha olefins.
- Such first polymer can be homopolymer polypropylene but is more preferably a random copolymer of units derived from propylene and from 0.1 to 10% of units derived from ethylene and/or one or more alpha-olefin monomers having from four to eight carbon atoms.
- the limits as to the amount of comonomer will depend in part upon the polymerization method, including catalyst selection (single site, metallocene, post metallocene, Ziegler-Natta, etc.) chosen.
- the first polymer should have a melt flow rate ("MFR") of from 0.5 to 25 g/10 min (as determined according to ASTM D1238, 2.16 kg, 230°C), more preferably from 2 to 1 g/10 min.
- MFR melt flow rate
- the particular MFR selected will depend in part on the intended fabrication methods such as blown film, extrusion coating, sheet extrusion, or cast film processes.
- the first polymer may have a density (as determined according to ASTM D-792) from 0.890 to 0.902 g/cm 3 .
- the first polymer should have a melting point (as determined according to the DSC method described below) of at least 125°C, more preferably at least 130°C or 135°C.
- the first outer layer may optionally contain up to 5 percent (by weight of the first outer layer) of an elastomeric propylene-based polymer or "EPBP".
- EPBPs comprise at least one copolymer with at least 50 weight percent of units derived from propylene and at least 5 weight percent of units derived from a comonomer other than propylene, preferably ethylene.
- Suitable elastomeric propylene based polymers include the propylene based plastomers or elastomers ("PBPE's") taught in WO03/040442 , and WO/2007/024447 .
- PBPE's propylene based plastomers or elastomers
- Of particular interest for use in the present invention are EPBP's having a molecular weight distribution of less than 3.5, including reactor grade PBPE's.
- reactor grade refers to a polyolefin resin whose molecular weight distribution (MWD) or polydispersity has not been substantially altered after polymerization.
- M w and M n are determined according to methods known in the art using conventional GPC.
- the preferred EPBP will have a heat of fusion (as determined using the DSC method described in WO2007/024447 ) less than 90 Joules/gm, preferably less than 70 Joules/gm, more preferably less than 50 Joules/gm.
- the EPBP has from 3 to 15 percent of ethylene, or from 5 to 14 percent of ethylene, or 7 to 12 percent ethylene, by weight of the EPBP.
- comonomers which may be used instead of, or in addition to the preferred ethylene comonomer in the EPBP include C 4-20 ⁇ -olefins, C 4-20 dienes, styrenic compounds and the like.
- the comonomer is at least one of ethylene and a C 4-12 ⁇ -olefin such as 1-hexene or 1-octene.
- the remaining units of the copolymer are derived only from ethylene.
- the amount of comonomer other than ethylene in the propylene based elastomer or plastomer is a function of, at least in part, the comonomer and the desired heat of fusion of the copolymer.
- the comonomer is ethylene
- typically the comonomer-derived units comprise not in excess of 15 wt % of the copolymer.
- the minimum amount of ethylene-derived units is typically at least 3, preferably at least 5 and more preferably at least 9, wt % based upon the weight of the copolymer.
- the polymer comprises at least one other comonomer other than ethylene, then the preferred composition would have a heat of fusion approximately in the range of a propylene-ethylene copolymer with 3 to 20 wt.% ethylene.
- the EPBPs of this invention can be made by any process, and includes copolymers made by CGC (Constrained Geometry Catalyst), metallocene, and nonmetallocene, metal-centered, heteroaryl ligand catalysis. These copolymers include random, block and graft copolymers although preferably the copolymers are of a random configuration.
- Exemplary propylene copolymers include Exxon-Mobil VISTAMAXXTM polymer, and VERSIFYTM propylene/ethylene elastomers and plastomers by The Dow Chemical Company.
- the density of the propylene based elastomers or plastomers of this invention is typically at least 0.850, can be at least 0.860 and can also be at least 0.865 grams per cubic centimeter (g/cm 3 ) as measured by ASTM D-792. Preferably the density is less than 0.89 g/cc. In general the lower the density, the lower the haze.
- the weight average molecular weight (Mw) of the propylene based elastomers or plastomers of this invention can vary widely, but typically it is between 10,000 and 1,000,000 (with the understanding that the only limit on the minimum or the maximum M w is that set by practical considerations).
- Mw weight average molecular weight
- the minimum Mw is about 20,000, more preferably about 25,000.
- the polydispersity of the elastomeric propylene based polymers of this invention is typically between 2 and 5. In general for low haze, it is preferred to use material with a narrow polydispersity.
- “Narrow polydispersity”, “narrow molecular weight distribution”, “narrow MWD” and similar terms mean a ratio (M w /M n ) of weight average molecular weight (M w ) to number average molecular weight (M n ) of less than 3.5, can be less than 3.0, can also be less than 2.8, can also be less than 2.5.
- the EPBPs for use in the first outer layer of the present invention ideally have an MFR of from 0.5 to 25 g/10min, preferably from 1 to 15, more preferably from 2 to 10.
- MFR for copolymers of propylene and ethylene and/or one or more C 4 -C 20 ⁇ -olefins is measured according to ASTM D-1238, condition L (2.16 kg, 230 degrees C).
- the multilayer films of the present invention further comprise an inner portion which is adjacent to the first outer layer.
- the inner portion may comprise a single layer or multiple layers, including microlayers.
- At least one layer of the inner portion comprises an EPBP as described above.
- at least one layer of the inner portion comprises a second polymer, wherein the second polymer is selected from the group consisting of high pressure low density polyethylene, high density polyethylene, ethylene acrylic acid copolymers, ethylene (meth) acrylic acid copolymers and combinations thereof.
- the second polymer may be together with the EPBP in the same layer or may be in a separate layer.
- the second polymer for use in the inner portion is selected from the group consisting of high pressure low density polyethylene, high density polyethylene, ethylene acrylic or (meth) acrylic acid copolymers and combinations thereof.
- high pressure low density polyethylene may also be referred to as "LDPE”, "high pressure ethylene polymer” or “highly branched polyethylene” and is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 100 MPa (14,500 psi) with the use of free-radical initiators, such as peroxides (see for example US 4,599,392 ).
- the LDPE if present, has a melt index (as determined according to ASTM D1238, 2.16 kg, 190°C) of from 0.5 to 35 g/10 min, more preferably from 2 to 10 g/ 10 min, and a density (as determined according to ASTM D-792) of from 0.915 to 0.935 g/cm 3 , preferably from 9.915 to 0.930.
- the term "high density polyethylene” or "HDPE" for purposes of this invention indicates linear polyethylene having a density greater than 0.940 g/cm 3 .
- the preferred HDPE has a melt index of from 0.5 to 10 g/10 min, more preferably from 2 to 10 g/10 min.
- EAA Ethylene acrylic copolymers
- EAA ethylene (meth) acrylic acid copolymers
- EAA or EMAA ethylene (meth) acrylic acid copolymers
- Preferred EAA or EMAA copolymers comprise from 3 to 20 percent by weight of units derived from the carboxylic acid copolymer.
- Suitable carboxyl-containing polymers include those sold under the trade name PRIMACORTM by the Dow Chemical Company.
- the EPBP comprise from 5 to 80 percent by weight of the layer, preferably from 30 to 80%, more preferably from 40 to 80%.
- the second polymer comprises from 20 to 60%.
- the random copolymer polypropylene resin is present in an amount of from 30 to 70 percent by weight of the layer, more preferably from 40 to 70%, still more preferably from 50 to 70% and/or homopolymer polypropylene preferably in an amount of from 5 to 10 percent by weight of the layer.
- each layer consists essentially of the pure EPBP or pure second polymer together with any additives.
- no blending morphology to create immiscible phases is involved, and thus fluctuations from minor variations in the fabrication process are minimized.
- the inner portion of the films of this embodiment of the present invention may comprise as few as two separate layers, but may also comprise a series of microlayers.
- Microlayers refers to sequences comprising a number, n, of repeating units, each repeating unit comprising at least two microlayers, (a) and (b), wherein one layer comprises PBPE and the other layer comprises the second polymer, such that the resulting structure has the formula [(a)(b)] n .
- "n" is defined by the multiplicator feedblock of the microlayer extruder.
- the repeating microlayer sequence may also optionally contain one or more additional repeating layers layers (c), (d), etc., or a non-repeating layer commonly called an encapsulating layer.
- the overall thickness can be similar to classical blown or cast films, for example 25 to 200 ⁇ m (microns).
- the ratios of the individual layers can be adjusted depending on the desired characteristics of the film but typically the ratios of A/B, A/C and B/C are in the range of from 0.2 to 0.8, and the ratio of the encapsulating layer (if present) to the repeating portion of the microlayer film is typically between 0.025 to 0.8.
- the multilayer films of the present invention further comprise a second outer layer arranged so that the inner portion is encapsulated between the first outer layer and the second outer layer. It should be understood that the term "encapsulate” as used herein refers to the planar surfaces; it is not necessary that the edges of the inner portion are also encapsulated by the first outer layer and second outer layer.
- the second outer layer comprises a third polymer, wherein said third polymer is selected from the group consisting of homopolymer polypropylene, random copolymer polypropylene and impact copolymer polypropylene and blends thereof.
- the preferences described for the first polymer are applicable for the third polymer, and in fact the third polymer may be the same as the first polymer.
- the MFR of the third polymer be from 0.5 to 35 g/10 min (as determined according to ASTM D1238, 2.16 kg, 230°C), more preferably from 2 to 10 g/10 min.
- the particular MFR selected will depend in part on the intended fabrication methods such as blown film, extrusion coating, sheet extrusion, or cast film processes.
- the multilayered films of the present invention may contain one or more additional layers to provide additional functionality.
- layers comprising ethylene vinyl alcohol polymers or polyamide polymers may be added to provide additional structural stability and/or barrier properties.
- the first outer layer has a thickness less than 30 ⁇ m (microns), preferably less than 20 ⁇ m (microns), more preferably 10 ⁇ m (microns) or less.
- the thickness of first outer layer determines force needed to initiate burst. Accordingly thinner films will require less force to initiate the burst. Once burst has been initiated, the film will be easy-opening, theoretically according to either the cohesive failure or delamination mechanism as described above. However, it should also be understood that thinner films will be more susceptible to damage during the retort process. Accordingly the first outer layer thickness should be optimized to achieve a proper balance of these properties.
- the film have a total thickness of less than 200 ⁇ m (microns), more preferably less than 150 ⁇ m (microns).
- HIT Heat Seal Initiation Temperature
- Burst peak Strength (N/15 mm) is determined according to ASTM F2029-00 with a visual inspection of the resulting seal curve, to determine the peak seal strength over full sealing temperature range.
- Peel Plateau Strength (N/15mm) is determined according to ASTM F2029-00 with a visual inspection of the resulting seal curve, section of seal curve after (peak), determination of temperature range at which seal strength variation is less than 2N/15mm over the range.
Description
- The invention relates to a polyolefin-based heat sealable, retortable easy opening seal. The invention also relates to methods of making and using the heat sealable, retortable easy opening seal.
- Heat sealable and easy-opening films are employed on a large scale for temporarily closing containers that include, for example, food products. During use, a consumer tears away the peelable film. To gain consumer acceptance, a number of characteristics associated with a heat sealable and peelable film are desired.
- Heat sealable films must be capable of being sealed upon the application of heat. During typical sealing processes, the backing or web layer of the film comes into direct contact with a heated surface such as a sealing jaw. Heat is thus transferred through the backing layer of the film to melt and fuse the inner sealant layer to form a seal. Accordingly the backing layer generally has a higher melting temperature than the inner sealant layer so that the backing layer of the film does not substantially melt and therefore does not stick to the heated surface.
- Moreover, if the package to be sealed is designed to contain food, particularly unrefrigerated food, then in order for the product to have an acceptable shelf life (for example at least six months) the seal should be capable of surviving a retort operation. A typical retort process subjects the sealed package to a temperature of 100°C. to 135°C. for 20 to 60 minutes or even up to 100 minutes, depending on the size of the container. During the retort process, gases are generated within the package and pressure increases greatly. Although the retort system may include an over pressure to help balance the package internal pressures, the net result will still be a pressurized package during retorting. Thus, the films used to seal the container must be sufficiently strong to withstand the increased internal pressure and the elevated temperatures.
- Because of the need to withstand such pressures, seals used in retort applications are typically difficult to open at room temperature using average manual force. It would be desirable to have a heat sealable film which could withstand the conditions of retort applications yet still be easily opened manually by a consumer. The force required to pull a seal apart is called "seal strength" or "heat seal strength" which can be measured in accordance with ASTM F88-94. The desired seal strength varies according to specific end user applications. For flexible packaging applications, such as cereal liners, snack food packages, cracker tubes and cake mix liners, the seal strength desired is generally in the range of 0.18-1.6 kilograms per centimeter. For example, for easy-open cereal box liners, a seal strength in the range of 0.35-0.52 kilograms per centimeter is commonly specified, although specific targets vary according to individual manufactures requirements. In addition to flexible packaging application, a sealable and peelable film can also be used in rigid package applications, such as lids for convenience items (e.g., snack food such as puddings) and medical devices. Typical rigid packages have a seal strength of 0.18-0.9 kilograms per centimeter. The seal layer can be on the lid or on the container or both.
- Another desired property for the heat-sealable films is adequate "hot tack". After the film is removed from contact with the heated surface and/or the retort process, the film is cooled to room temperature. Before the inner sealant layer is cooled to room temperature, it should be able to maintain its seal integrity. The ability of an adhesive or sealant layer to resist creep of the seal while it is still in a warm or molten state is generally referred to as "hot tack." To form a good seal, the hot tack of the sealable and peelable film should be adequate.
- It is also desirable to have a low heat seal initiation temperature which helps to ensure fast packaging line speeds and a broad sealing window which could accommodate variability in process conditions, such as pressure and temperature. A broad sealing window also enables high speed packaging of heat sensitive products, as well as, provides a degree of forgiveness for changes in packaging or filling speeds.
- Additional desired characteristics for heat sealable films include a low coefficient of friction and good abuse resistance. A low coefficient of friction ensures that the sealant layer can be processed smoothly and efficiently on fabrication and packaging equipment and is particularly important for vertical form-fill-and-seal packaging. Good abuse resistance and toughness is desired, for example, in cereal box liners to withstand tears and punctures from irregularly-shaped, rigid cereals. Additional characteristics include taste and odor performance and barrier or transmission properties.
- It has been discovered that certain multilayer films will achieve one or more of the above stated goals, and thus be particularly well suited for retort applications. The multilayer film comprises a first outer layer which is heat sealable. The first outer layer comprises from 95 to 100 percent (by weight of the first outer layer) of a first polymer, said first polymer being derived from propylene monomer and optionally one or more comonomers selected from the group consisting of ethylene and C4-C8 alpha olefins. The first polymer has a melting point of at least 125°C. The multilayer film further comprises an inner portion adjacent to the first outer layer. The inner portion may be a single layer or may comprise several layers. At least one layer of the inner portion comprises an elastomeric propylene based polymer ("EPBP"). Further at least one layer of the inner portion comprises a second polymer, wherein the second polymer is selected from the group consisting of high pressure low density polyethylene, high density polyethylene, ethylene acrylic acid copolymers, ethylene (meth) acrylic acid copolymers and combinations thereof. The second polymer may be together with the EPBP in the same layer or may be in a separate layer. It is also contemplated that the inner portion may optionally comprise one or more additional layers, which may or may not contain EPBP or the second polymer. The multilayer film further comprises a second outer layer arranged so that the inner portion is encapsulated between the first outer layer and the second outer layer. The second outer layer comprises a third polymer, wherein said third polymer is selected from the group consisting of homopolymer polypropylene, random copolymer polypropylene and impact copolymer polypropylene and blends thereof.
-
U.S. Patent Publication No. 2004/0151932 to Galloway is directed to sealant films comprising a first sealant layer which readily and easily delaminates or peels from a second adjacent film layer. The first sealant layer and the second adjacent layer of the sealant film comprise propylene or ethylene moieties wherein the propylene or ethylene moieties may be homopolymers or copolymers. The film structures can be used independently, or laminated to a second film structure wherein the second film structure may comprise a single layer or multiple layers. The sealant films can be heat sealed to a packaging component, such as a tray either as a single film structure or as a laminate comprising a second film structure. The sealant film structures may be used as retortable lidstock. The sealant films disclosed by Galloway do not however possess the desired retort properties. - The term "polymer", as used herein, refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term "homopolymer", usually employed to refer to polymers prepared from only one type of monomer as well as "copolymer" which refers to polymers prepared from two or more different monomers.
- "Melt strength" which is also referred to in the relevant art as "melt tension" is defined and quantified herein to mean the stress or force (as applied by a wind-up drum equipped with a strain cell) required to draw a molten extrudate at a haul-off velocity at which the melt strength plateaus prior to breakage rate above its melting point as it passes through the die of a standard plastometer such as the one described in ASTM D1238-E. Melt strength values, which are reported herein in centi-Newtons (cN), are determined using a Gottfert Rheotens at 190°C.
- The present invention relates to a multilayer film particularly well-suited for heat seals used in retort applications. The multilayer film comprises a first outer layer which is heat sealable. The first outer layer comprises from 95 to 100 percent (by weight of the first outer layer) of a first polymer, said first polymer being derived from propylene monomer and optionally one or more comonomers selected from the group consisting of ethylene and C4-C8 alpha olefins. Such first polymer can be homopolymer polypropylene but is more preferably a random copolymer of units derived from propylene and from 0.1 to 10% of units derived from ethylene and/or one or more alpha-olefin monomers having from four to eight carbon atoms. The limits as to the amount of comonomer will depend in part upon the polymerization method, including catalyst selection (single site, metallocene, post metallocene, Ziegler-Natta, etc.) chosen. The first polymer should have a melt flow rate ("MFR") of from 0.5 to 25 g/10 min (as determined according to ASTM D1238, 2.16 kg, 230°C), more preferably from 2 to 1 g/10 min. The particular MFR selected will depend in part on the intended fabrication methods such as blown film, extrusion coating, sheet extrusion, or cast film processes. The first polymer may have a density (as determined according to ASTM D-792) from 0.890 to 0.902 g/cm3. The first polymer should have a melting point (as determined according to the DSC method described below) of at least 125°C, more preferably at least 130°C or 135°C.
- The first outer layer may optionally contain up to 5 percent (by weight of the first outer layer) of an elastomeric propylene-based polymer or "EPBP". EPBPs comprise at least one copolymer with at least 50 weight percent of units derived from propylene and at least 5 weight percent of units derived from a comonomer other than propylene, preferably ethylene. Suitable elastomeric propylene based polymers include the propylene based plastomers or elastomers ("PBPE's") taught in
WO03/040442 WO/2007/024447 . Of particular interest for use in the present invention are EPBP's having a molecular weight distribution of less than 3.5, including reactor grade PBPE's. The term "reactor grade" refers to a polyolefin resin whose molecular weight distribution (MWD) or polydispersity has not been substantially altered after polymerization. The term molecular weight distribution or "MWD" is defined as the ratio of weight average molecular weight to number average molecular weight (Mw/Mn). Mw and Mn are determined according to methods known in the art using conventional GPC. The preferred EPBP will have a heat of fusion (as determined using the DSC method described inWO2007/024447 ) less than 90 Joules/gm, preferably less than 70 Joules/gm, more preferably less than 50 Joules/gm. When the preferred comonomer ethylene is used, the EPBP has from 3 to 15 percent of ethylene, or from 5 to 14 percent of ethylene, or 7 to 12 percent ethylene, by weight of the EPBP. - Other comonomers which may be used instead of, or in addition to the preferred ethylene comonomer in the EPBP include C4-20 α-olefins, C4-20 dienes, styrenic compounds and the like. Preferably the comonomer is at least one of ethylene and a C4-12 α-olefin such as 1-hexene or 1-octene. Preferably, the remaining units of the copolymer are derived only from ethylene. The amount of comonomer other than ethylene in the propylene based elastomer or plastomer is a function of, at least in part, the comonomer and the desired heat of fusion of the copolymer. If the comonomer is ethylene, then typically the comonomer-derived units comprise not in excess of 15 wt % of the copolymer. The minimum amount of ethylene-derived units is typically at least 3, preferably at least 5 and more preferably at least 9, wt % based upon the weight of the copolymer. If the polymer comprises at least one other comonomer other than ethylene, then the preferred composition would have a heat of fusion approximately in the range of a propylene-ethylene copolymer with 3 to 20 wt.% ethylene.
- The EPBPs of this invention can be made by any process, and includes copolymers made by CGC (Constrained Geometry Catalyst), metallocene, and nonmetallocene, metal-centered, heteroaryl ligand catalysis. These copolymers include random, block and graft copolymers although preferably the copolymers are of a random configuration. Exemplary propylene copolymers include Exxon-Mobil VISTAMAXX™ polymer, and VERSIFY™ propylene/ethylene elastomers and plastomers by The Dow Chemical Company.
- The density of the propylene based elastomers or plastomers of this invention is typically at least 0.850, can be at least 0.860 and can also be at least 0.865 grams per cubic centimeter (g/cm3) as measured by ASTM D-792. Preferably the density is less than 0.89 g/cc. In general the lower the density, the lower the haze.
- The weight average molecular weight (Mw) of the propylene based elastomers or plastomers of this invention can vary widely, but typically it is between 10,000 and 1,000,000 (with the understanding that the only limit on the minimum or the maximum Mw is that set by practical considerations). For homopolymers and copolymers used in the manufacture of peelable seals, preferably the minimum Mw is about 20,000, more preferably about 25,000.
- The polydispersity of the elastomeric propylene based polymers of this invention is typically between 2 and 5. In general for low haze, it is preferred to use material with a narrow polydispersity. "Narrow polydispersity", "narrow molecular weight distribution", "narrow MWD" and similar terms mean a ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of less than 3.5, can be less than 3.0, can also be less than 2.8, can also be less than 2.5.
- The EPBPs for use in the first outer layer of the present invention ideally have an MFR of from 0.5 to 25 g/10min, preferably from 1 to 15, more preferably from 2 to 10. MFR for copolymers of propylene and ethylene and/or one or more C4-C20 α-olefins is measured according to ASTM D-1238, condition L (2.16 kg, 230 degrees C).
- The multilayer films of the present invention further comprise an inner portion which is adjacent to the first outer layer. The inner portion may comprise a single layer or multiple layers, including microlayers. At least one layer of the inner portion comprises an EPBP as described above. Further at least one layer of the inner portion comprises a second polymer, wherein the second polymer is selected from the group consisting of high pressure low density polyethylene, high density polyethylene, ethylene acrylic acid copolymers, ethylene (meth) acrylic acid copolymers and combinations thereof. The second polymer may be together with the EPBP in the same layer or may be in a separate layer. Without being bound to any particular theory, it is believed that including the second polymer in the same layer as the EPBP results in a burst cohesive failure mechanism as depicted in
Figure 1 whereas including the second polymer in a separate layer results in a burst delaminating failure mechanism as depicted inFigure 2 . - The second polymer for use in the inner portion is selected from the group consisting of high pressure low density polyethylene, high density polyethylene, ethylene acrylic or (meth) acrylic acid copolymers and combinations thereof. The term "high pressure low density polyethylene" may also be referred to as "LDPE", "high pressure ethylene polymer" or "highly branched polyethylene" and is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 100 MPa (14,500 psi) with the use of free-radical initiators, such as peroxides (see for example
US 4,599,392 ). It is preferred that the LDPE, if present, has a melt index (as determined according to ASTM D1238, 2.16 kg, 190°C) of from 0.5 to 35 g/10 min, more preferably from 2 to 10 g/ 10 min, and a density (as determined according to ASTM D-792) of from 0.915 to 0.935 g/cm3, preferably from 9.915 to 0.930. The term "high density polyethylene" or "HDPE" for purposes of this invention indicates linear polyethylene having a density greater than 0.940 g/cm3. The preferred HDPE has a melt index of from 0.5 to 10 g/10 min, more preferably from 2 to 10 g/10 min. Ethylene acrylic copolymers ("EAA") or ethylene (meth) acrylic acid copolymers ("EMAA") refers to copolymers derived from ethylene acrylic acid or methacrylic acid, respectively. Preferred EAA or EMAA copolymers comprise from 3 to 20 percent by weight of units derived from the carboxylic acid copolymer. Suitable carboxyl-containing polymers include those sold under the trade name PRIMACOR™ by the Dow Chemical Company. - Where the EPBP is blended with the second polymer in at least one layer, the EPBP comprise from 5 to 80 percent by weight of the layer, preferably from 30 to 80%, more preferably from 40 to 80%. The second polymer comprises from 20 to 60%. The random copolymer polypropylene resin, is present in an amount of from 30 to 70 percent by weight of the layer, more preferably from 40 to 70%, still more preferably from 50 to 70% and/or homopolymer polypropylene preferably in an amount of from 5 to 10 percent by weight of the layer.
- For the embodiments where the EPBP and second polymer are in separate layers, it is preferred that each layer consists essentially of the pure EPBP or pure second polymer together with any additives. In such embodiments, no blending morphology to create immiscible phases is involved, and thus fluctuations from minor variations in the fabrication process are minimized. It is contemplated that the inner portion of the films of this embodiment of the present invention may comprise as few as two separate layers, but may also comprise a series of microlayers. "Microlayers" refers to sequences comprising a number, n, of repeating units, each repeating unit comprising at least two microlayers, (a) and (b), wherein one layer comprises PBPE and the other layer comprises the second polymer, such that the resulting structure has the formula [(a)(b)]n. "n" is defined by the multiplicator feedblock of the microlayer extruder. The repeating microlayer sequence may also optionally contain one or more additional repeating layers layers (c), (d), etc., or a non-repeating layer commonly called an encapsulating layer. The overall thickness can be similar to classical blown or cast films, for example 25 to 200 µm (microns). The ratios of the individual layers can be adjusted depending on the desired characteristics of the film but typically the ratios of A/B, A/C and B/C are in the range of from 0.2 to 0.8, and the ratio of the encapsulating layer (if present) to the repeating portion of the microlayer film is typically between 0.025 to 0.8. The multilayer films of the present invention further comprise a second outer layer arranged so that the inner portion is encapsulated between the first outer layer and the second outer layer. It should be understood that the term "encapsulate" as used herein refers to the planar surfaces; it is not necessary that the edges of the inner portion are also encapsulated by the first outer layer and second outer layer.
- The second outer layer comprises a third polymer, wherein said third polymer is selected from the group consisting of homopolymer polypropylene, random copolymer polypropylene and impact copolymer polypropylene and blends thereof. The preferences described for the first polymer are applicable for the third polymer, and in fact the third polymer may be the same as the first polymer. In general it is preferred that the MFR of the third polymer be from 0.5 to 35 g/10 min (as determined according to ASTM D1238, 2.16 kg, 230°C), more preferably from 2 to 10 g/10 min. The particular MFR selected will depend in part on the intended fabrication methods such as blown film, extrusion coating, sheet extrusion, or cast film processes.
- Optionally, the multilayered films of the present invention may contain one or more additional layers to provide additional functionality. For example layers comprising ethylene vinyl alcohol polymers or polyamide polymers may be added to provide additional structural stability and/or barrier properties.
- It is preferred that the first outer layer has a thickness less than 30 µm (microns), preferably less than 20 µm (microns), more preferably 10 µm (microns) or less. The thickness of first outer layer determines force needed to initiate burst. Accordingly thinner films will require less force to initiate the burst. Once burst has been initiated, the film will be easy-opening, theoretically according to either the cohesive failure or delamination mechanism as described above. However, it should also be understood that thinner films will be more susceptible to damage during the retort process. Accordingly the first outer layer thickness should be optimized to achieve a proper balance of these properties.
- It is preferred that the film have a total thickness of less than 200 µm (microns), more preferably less than 150 µm (microns).
- In order to demonstrate the utility of the present invention a series of multilayer films were made using the resins described in Table I
-
Table I Resins used in the examples) Resin Description Comonomer Melt index* (g/10 min) Density (g/cm3) MFR** (g/10min) Melting Point (ºC) A Random Copolymer Polypropylene Ethylene 0.900 2 144 B Impact Copolymer Polypropylene Ethylene 0.902 0.5 164 C Impact Copolymer Polypropylene Ethylene 0.900 0.8 164 D Homopolymer Polypropylene None 0.900 2.1 164 E High Pressure LDPE None 0.75 0.924 112 F High Pressure LDPE None 2 0.925 114 G High Pressure LDPE None 2 0.920 110 H PBPE 9%wt Ethylene 0.876 2 82 I PBPE 5%wt Ethylene 0.888 2 107 * at 190ºC under 2.16kg ** at 230ºC under 2.16kg - Haze (%) is determined according to ASTM D1003-11
- Heat Seal Initiation Temperature (HSIT) (ºC) is determined according to ASTMF2029-00 with a visual inspection of the resulting heat seal curve for the determination of temperature at which seal strength curve rises higher than 2 N/15mm.
- Burst peak Strength (N/15 mm) is determined according to ASTM F2029-00 with a visual inspection of the resulting seal curve, to determine the peak seal strength over full sealing temperature range.
- Peel Plateau Strength (N/15mm) is determined according to ASTM F2029-00 with a visual inspection of the resulting seal curve, section of seal curve after (peak), determination of temperature range at which seal strength variation is less than 2N/15mm over the range.
- Seal Window (°C) is determined according to ASTM F2029-00 with a visual inspection of the resulting seal curve to determine the temperature range in which all seal strengths are higher than 2 N/15 mm.
Table II -Examples of A) - Encapsulated cohesive peel layer for a burst cohesive failure mechanism Example 1 Example 2 Example 3 Film Structure A/B/C 70/20/10 A/B/C 70/20/10 A/B/C 70/20/10 Film thickness (µm) ((microns)) 100 100 100 Layer A 100% Resin A 100% Resin A 100% Resin A Layer B Compound: 50% Resin H + 50% Resin F Compound: 35% Resin A + 15% Resin H + 50% Resin F Compound: 33% Resin A + 2% Resin D + 15% Resin H + 50% Resin F Layer C 100% Resin A 100% Resin A 100% Resin A Layer D none none none Layer E none none none Failure mode Burst + Delaminating Failure Burst + Delaminating Failure Burst + Delaminating Failure Haze before Retort(%) 6 4 9 Haze after Retort (%) 16 13 15 Seal properties before Retort: HSIT (°C) 130 130 130 Burst peak Strength 8 - 10 N/15 mm (3 - 4 lb/in) 7 N/15 mm (2.8 lb/in) 7 N/15 mm (2.8 lb/in) Peel plateau Strength 4 N/15 mm (1.5 lb/in) 2 N/15 mm (0.8 lb/in) 2 N/15 mm (0.8 lb/in) Seal properties After Retort: HSIT (°C) 130 130 130 Burst peak Strength (N/15 mm) 8 - 10 N/15 mm (3 - 4 lb/in) 7 N/15 mm (2.8 lb/in) 7 N/15 mm (2.8 lb/in) Peel plateau Strength (N/15 mm) 4 N/15 mm (1.5 lb/in) 2 N/15 mm (0.8 lb/in) 2 N/15 mm (0.8 lb/in) Table II2 Example 4 Example 5 Example 6 Example 7 Example 8 Film Structure A/A/B/A 35/35/20/10 A/C/B/C 35/35/20/10 A/A/B/A 35/35/20/10 A/C/B/C 35/35/20/10 A/C/B/C 35/35/20/10 Film thickness (µm) ((microns)) 100 100 100 100 100 Layer A 100% Resin A 100% Resin A 100% Resin A 100% Resin A 100% Resin A Layer B Compound: 35% Resin A, 45% Resin E, 15 % Resin I, 5% Resin K Compound: 35% Resin A, 45% Resin E, 15 % Resin I, 5% Resin K Compound: 35% Resin A, 35% Resin E, 15 % Resin I, 15% Resin K Compound: 35% Resin A, 50% Resin E, 15% Resin I Compound: 55% Resin A, 30% Resin E, 15 % Resin I Layer C none 85% Resin A, 15% Resin K none 95% Resin A, 5% Resin J 95% Resin A, 5% Resin J Haze before Retort (%) 3.67 28.6 4.27 3.45 4.02 Haze after Retort (%) 13.6 38.7 14.3 13 14.5 Seal properties before Retort: HSIT (°C) 130 130 130 130 130 Burst peak Strength 7 N/15 mm (lb/in) 8 N/15 mm (lb/in) 12 N/15 mm (lb/in) 8 N/15 mm (lb/in) 10 N/15 mm (lb/in) Peel plateau Strength 2 N/15 mm (lb/in) 2 N/15 mm (lb/in) 1N/15 mm (lb/in) 2.5 N/15 mm (lb/in) 3 N/15 mm (lb/in) Seal properties After Retort: HSIT (°C) 130 130 130 130 130 Burst peak Strength 8 N/15 mm (lb/in) 9 N/15 mm (lb/in) 8.5 N/15 mm (lb/in) 9 N/15 mm (lb/in) 16 N/15 mm (lb/in) Peel plateau Strength 1 N/15 mm (lb/in) 1.5 N/15 mm (lb/in) 1.5 N/15 mm (lb/in) 2 N/15 mm (lb/in) 3 N/15 mm (lb/in) Table III Examples of B) - Encapsulated delamination peel layers for a burst delaminating failure mechanism Example 9 Example 10 Film Structure A/B/C/D/E 40/10/30/10/10 A/B/C/D/E 40/10/30/10/10 Film thickness (µm) ((microns)) 100 100 Layer A 100% Resin A 100% Resin A Layer B 100% Resin I 100% Resin H Layer C 100% Resin E 100% Resin E Layer D 100% Resin I 100% Resin H Layer E 100% Resin A 100% Resin A Failure mode Burst + Delaminating Failure Burst + Delaminating Failure Haze before Retort (%) 5 8 Haze after Retort (%) 16 20 Seal properties before Retort: HSIT (°C) 130 130 Burst peak Strength 8 - 10 N/15 mm (3 - 4 lb/in) 8 - 10 N/15 mm (3 - 4 lb/in) Peel plateau Strength 0.5 N/15 mm (0.2 lb/in) 1 N/15 mm (0.4 lb/in) Seal properties After Retort: HSIT (°C) 130 130 Burst peak Strength 8 N/15 mm (3 lb/in) 5 N/15 mm (2 lb/in) Peel plateau Strength 0.5 N/15 mm (0.2 lb/in) 0.5 N/15 mm (0.2 lb/in)
Claims (15)
- A multilayer film comprising:a. a first outer layer which is heat sealable, said first outer layer comprising from 95 to 100 percent by weight of the first outer layer of a first polymer, said first polymer being derived from propylene and optionally one or more comonomers selected from the group consisting of ethylene and C4-C8 alpha olefins, said first polymer having a melting point of at least 125°C;b. an inner portion adjacent to the first outer layer, said inner portion comprising (i) from 5 to 80 percent by weight of the inner portion of an elastomeric propylene based polymer; (ii) from 30 to 70 percent by weight of the inner portion of a random copolymer derived from propylene and one or more additional comonomers selected from the group consisting of ethylene, and C4-C8 alpha olefins; and (iii) from 20 to 60 percent by weight of the inner portion of a second polymer, wherein the second polymer is selected from the group consisting of high pressure low density polyethylene, high density polyethylene, ethylene acrylic acid copolymers, ethylene (meth) acrylic acid copolymers and combinations thereof;c. optionally one or more additional layers; andd. a second outer layer arranged so that the inner portion is encapsulated between the first outer layer and the second outer layer, said second outer layer comprising a third polymer, wherein said third polymer is selected from the group consisting of homopolymer polypropylene, random copolymer polypropylene and impact copolymer polypropylene and blends thereof.
- The film of claim 1 wherein the inner portion further comprises:a. from 5 to 10 percent by weight of the inner portion of a homopolypropylene.
- The film of claim 1 wherein the elastomeric propylene based polymer has an MFR of from 2 to 25 g/10 min determined according to ASTM D1238 at 2.16 kg and at 230°C, and a density of from 0.850 to 0.890 g/cm3.
- The film of claim 1 wherein the random copolymer has an MFR of from 0.5 to 5 g/10 min determined according to ASTM D1238 at 2.16 kg and at 230°C, and a density of from 0.90 to 0.902 g/cm3.
- The film of claim 1 wherein the third polymer is homopolymer polypropylene and wherein the homopolymer polypropylene has an MFR of from 0.5 to 10 g/10 min determined according to ASTM D1238 at 2.16 kg and at 230°C.
- The film of claim 1 wherein the second polymer is a high pressure low density polyethylene and has an MI of from 0.5 to 35 g/10 min determined according to ASTM D1238 at 2.16 kg and at 230°C, and a density of from 0.915 to 0.932 g/cm3.
- The film of claim 1 wherein the second polymer is a high density polyethylene and has an MI of from 0.5 to 10 g/10 min determined according to ASTM D1238 at 2.16 kg and at 230°C, and a density of from 0.94 to 0.96 g/cm3.
- The film of claim 1 wherein the second polymer is an ethylene acrylic acid copolymer or an ethylene (meth)acrylic acid copolymer and has an MI of from 0.5 to 10 g/10 min determined according to ASTM D1238 at 2.16 kg and at 230°C, and a comonomer content of from 3 to 20 percent by weight of the ethylene acrylic acid copolymer or ethylene (meth)acrylic acid copolymer.
- The film of claim 1 wherein the first outer layer further comprises from 0.1 to 5 percent by weight of the first outer layer, of an elastomeric propylene based polymer, which may be the same or different from the elastomeric propylene based polymer(s) used in the inner portion.
- The film of Claim 1 wherein the first polymer has an MFR of from 0.5 to 5 g/10 min determined according to ASTM D1238 at 2.16 kg and at 230°C, and a density of from 0.90 to 0.902 g/cm3.
- The film of claim 1 wherein the third polymer has an MFR of from 0.5 to 5 g/10 min determined according to ASTM D1238 at 2.16 kg and at 230°C.
- The film of claim 1 wherein the second outer layer further comprises a barrier structure comprised of ethyl vinyl alcohol or a polyamide.
- The film of claim 12 wherein the barrier structure is coextruded as a separate layer.
- The film of claim 1 wherein the film further comprises one or more non-surface layers in addition to the inner portion.
- The film of claim 1 wherein the first polymer is a polypropylene.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL12815966T PL2797742T3 (en) | 2011-12-28 | 2012-12-27 | Retortable easy opening seals for packaging film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161580815P | 2011-12-28 | 2011-12-28 | |
PCT/US2012/071825 WO2013101931A1 (en) | 2011-12-28 | 2012-12-27 | Retortable easy opening seals for packaging film |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2797742A1 EP2797742A1 (en) | 2014-11-05 |
EP2797742B1 true EP2797742B1 (en) | 2017-07-05 |
Family
ID=47559734
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12815966.2A Active EP2797742B1 (en) | 2011-12-28 | 2012-12-27 | Retortable easy opening seals for packaging film |
Country Status (11)
Country | Link |
---|---|
US (1) | US20140377548A1 (en) |
EP (1) | EP2797742B1 (en) |
JP (1) | JP6207526B2 (en) |
CN (1) | CN104136215B (en) |
BR (1) | BR112014015813B1 (en) |
ES (1) | ES2639287T3 (en) |
IN (1) | IN2014CN04780A (en) |
MX (1) | MX340400B (en) |
PL (1) | PL2797742T3 (en) |
RU (1) | RU2014130753A (en) |
WO (1) | WO2013101931A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10099453B2 (en) * | 2014-10-20 | 2018-10-16 | Dow Global Tchnologies LLC | Multilayer structure, a film made therefrom and a package formed therefrom |
AR109065A1 (en) | 2016-07-28 | 2018-10-24 | Dow Global Technologies Llc | MULTI-PAPER STRUCTURES, MULTI-PAPER FILMS AND FORMED CONTAINERS FROM THEM |
WO2018118068A1 (en) | 2016-12-22 | 2018-06-28 | Bemis Company, Inc. | Packaging films with improved hot-tack performance |
WO2019018127A1 (en) | 2017-07-18 | 2019-01-24 | Dow Global Technologies Llc | Resins, multilayer films and packages comprising the same |
SG10201903296WA (en) * | 2019-04-12 | 2020-09-29 | Thai Polyethylene Co Ltd | A Polypropylene Composition for Retort Packaging Application |
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US4599392A (en) | 1983-06-13 | 1986-07-08 | The Dow Chemical Company | Interpolymers of ethylene and unsaturated carboxylic acids |
CA2103401C (en) * | 1992-11-19 | 2002-12-17 | Mamoru Takahashi | Ethylene copolymer composition |
EP0756931B2 (en) * | 1995-07-31 | 2011-06-22 | Kureha Corporation | Multilayer film |
BR9612569A (en) * | 1996-03-21 | 1999-12-28 | Sengewald Verpackungen Gmbh | Multilayered sheet, process for its preparation and application |
JPH09327889A (en) * | 1996-06-11 | 1997-12-22 | Sekisui Chem Co Ltd | Sealant film |
US5759648A (en) * | 1996-07-05 | 1998-06-02 | Viskase Corporation | Multilayer plastic film, useful for packaging a cook-in foodstuff |
JPH11192679A (en) * | 1998-01-05 | 1999-07-21 | Asahi Chem Ind Co Ltd | Heat-shrinkable multilayer film |
JP4358339B2 (en) * | 1999-01-14 | 2009-11-04 | グンゼ株式会社 | Peelable peelable heat-adhesive laminated film and bag body thereof |
US6479160B1 (en) * | 2001-03-09 | 2002-11-12 | Honeywell International Inc. | Ultra high oxygen barrier films and articles made therefrom |
ES2282515T3 (en) | 2001-11-06 | 2007-10-16 | Dow Global Technologies Inc. | ISOTACTIC PROPYLENE COPOLYMER FIBERS, ITS PREPARATION AND USE. |
US7314669B2 (en) * | 2003-02-05 | 2008-01-01 | Pechiney Emballage Flexible Europe | Easy peel film structures |
JP4288107B2 (en) * | 2003-06-02 | 2009-07-01 | 日本ポリプロ株式会社 | Heat sterilized food packaging film |
US20080199673A1 (en) | 2005-08-19 | 2008-08-21 | Allgeuer Thomas T | Propylene Based Meltblown Nonwoven Layers and Composite Structures |
KR20080068043A (en) * | 2005-10-05 | 2008-07-22 | 다우 글로벌 테크놀로지스 인크. | Polyolefin based peelable seals |
JP5313917B2 (en) * | 2006-12-21 | 2013-10-09 | ダウ グローバル テクノロジーズ エルエルシー | LAMINATED FILM, PACKAGE MADE THEREFROM, AND METHOD FOR MANUFACTURING THE SAME |
JP4877062B2 (en) * | 2007-05-15 | 2012-02-15 | Dic株式会社 | Coextruded multilayer film and packaging material comprising the film |
JP2009154332A (en) * | 2007-12-25 | 2009-07-16 | Japan Polyethylene Corp | Laminate |
EP2241438B1 (en) * | 2008-02-08 | 2014-03-26 | Mitsui Chemicals, Inc. | Film for thermal sterilization packaging |
PL2416961T3 (en) * | 2009-04-10 | 2023-01-09 | Dow Global Technologies Llc | High performance sealable coextruded biaxially oriented polypropylene film |
ES2628777T3 (en) * | 2009-05-08 | 2017-08-03 | Dow Global Technologies Llc | Multilayer films based on heat sealable and oriented polypropylene for retractable applications |
US9108391B2 (en) * | 2010-05-31 | 2015-08-18 | Otsuka Pharmaceutical Factory, Inc. | Multilayer film and bag formed of multilayer film |
-
2012
- 2012-12-27 JP JP2014550463A patent/JP6207526B2/en active Active
- 2012-12-27 IN IN4780CHN2014 patent/IN2014CN04780A/en unknown
- 2012-12-27 RU RU2014130753A patent/RU2014130753A/en not_active Application Discontinuation
- 2012-12-27 ES ES12815966.2T patent/ES2639287T3/en active Active
- 2012-12-27 WO PCT/US2012/071825 patent/WO2013101931A1/en active Application Filing
- 2012-12-27 EP EP12815966.2A patent/EP2797742B1/en active Active
- 2012-12-27 CN CN201280070675.2A patent/CN104136215B/en active Active
- 2012-12-27 PL PL12815966T patent/PL2797742T3/en unknown
- 2012-12-27 US US14/364,333 patent/US20140377548A1/en not_active Abandoned
- 2012-12-27 MX MX2014007927A patent/MX340400B/en active IP Right Grant
- 2012-12-27 BR BR112014015813-4A patent/BR112014015813B1/en active IP Right Grant
Also Published As
Publication number | Publication date |
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RU2014130753A (en) | 2016-02-20 |
EP2797742A1 (en) | 2014-11-05 |
IN2014CN04780A (en) | 2015-09-18 |
BR112014015813B1 (en) | 2020-12-22 |
MX2014007927A (en) | 2014-07-30 |
CN104136215A (en) | 2014-11-05 |
CN104136215B (en) | 2016-10-26 |
MX340400B (en) | 2016-07-07 |
US20140377548A1 (en) | 2014-12-25 |
BR112014015813A2 (en) | 2017-06-13 |
JP6207526B2 (en) | 2017-10-04 |
PL2797742T3 (en) | 2017-12-29 |
JP2015507565A (en) | 2015-03-12 |
WO2013101931A1 (en) | 2013-07-04 |
ES2639287T3 (en) | 2017-10-26 |
BR112014015813A8 (en) | 2017-07-04 |
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